Process of making formates.



No. 975,055., PATBNTED DEG, s1, 1907.

* mms @L K. P. MUBLRUL PROCESS 0F MAKING 'QRMATBS.' APPLIMTIQH FILED mm 11. 190e.

lll'o.

peoileation of .".liettere Patent,

applicati@ filed June ll., i906I Serial No. 321.129.

To all toller/t 'it may concern.'

Be it lrnovvn that vve, @linearen lrris and librar l). lllelliiiior, citizens oi the United lltates, resii'ling, respectively, in

i Plains, county ol.2 lllestchester, and. State ol3 New York, and in lrlashington, llistrict of lColumbia., haye invented certain new and uselul lmprovements in Processes oiililalring lformtmtes and we hereby declare the llollovvle ing` to be a lull, clear, and exact description ol the saine.

'lhis invention relates to processes of malring Alorrnates and consists in a method of synthesizing* formatos by the reaction ol carbon l Amonoirir upon substantially insoluble metallic carbonatos, and similar substantially insoluble basic bodies, under" certain novel conditions; all as more Vfully hereinafterset `lordi, matters oi novelty being particularly pointed out in the appended claims.

Forrnie acid, lllCOOH, has the same empirical composition as a molecule of water and a molecule of carbon inonoirid taken togetloer, and it has long been known that in the presence oil' soluble allralies, the monofn'd and Water would react together to 'lorin `formaties. The reaction however is'slow, the yield not good and the :formates ol' the only .bases hitherto deemed Well adapted, potassium` and sodium, are not particularly desirable coinrnercialljf since it is diliicult to produce jiormlc acid from them. 'lhe slowness and poor yield partly due to the tact that formater; are not very stable in alkaline solutions.

lt is the'ohject of the present invention to produce metallic iiormates, and particularly rarbonates oli the alkaline eartns or zinc 0X1 l,g

those ol' Athe allraline earth metals, by a simple, elieup and ready method enablingl l flo the production ol large yields from cheap raw materials and deliverlngg; lormates oli Y h dralt current containing carbon dioxld as an more commercial value. For his purpose there is prelf'erably used as a rau" nutterial a y metallic"carbonate insoluble in. water, Vand particularly one ol an alkaline earth metal;

relerably a precipitated4 carbonate. Being p `insoluble in water, these bodies do not have the stated detrimental etlfeet upon the pro duced 'liinmati-i, and a soluble el such pro-v duced l'orniate can bewithdrawn from time to time l'rom the excess of base Without danger ol coiita'mination by dissolved base. ln the ease of a precipitated carbonate, it is -of an eirtreme linenesa such as could only be prolllhite able lor making forinic acid.

duced l rom the natural carbonatos by laborious grinding', Such natural carbonates may hoireyer be used, though with less advantage. ln the case ol calcium carbonate, the line powder produced by air slaliing lime may also be used. lline division is very advantageous, although not absolutely necessary, facilitating chemical reaction aud-as permitting' suspension of the material in Water to secure ntim ate contact of the three reacting bodies, monoxid, water and base. rlhe carbonate used will ot course depend on the formate to be made, but ordinarily those .ol calcium, bariuin'and strontium are to be preferred since these bases yield insoluble suliates and oxalates and are therefore suit- Y liead earbonate is also suitable for the same reason. liead oXid, Zinc oXid or any other insoluble metallic ofrid rn ay be used in lieu ol` the ear bonate. tlaleium carbonate is however regarded particularly suitable because of the low molecular Weight of calcium and because "he precipitated carbonate is readily available as a irastirrproduct in many arts, for instance in the causticizing of soda, in the purification oi` Water, etc. illagnesium oxid and carbonate are also suitable To avoid production ol an impure 'formate solution which cannot be drawn oil substantially pure by simple settling, the basic body employed should be one which issubstantial ly insoluble in Water; that is one which is not soluble in water to the extent of more than a Yleu' lumdredths per cent., and, prefer ably, not to the extent of' more than a teiv thousamlths per cent., as in the ease oi the its a source of carbon inonoxid, producer ,gas is cheap and. suitable. Preferably the ,iras is made by leerling tue producer with a eudothermic constituent. Producer gas made with steam is much less suitable since it contains hydrogen, has relatively less carbon monoxid and generally contains an excessive amount of carbon dioXid. Producer made with a dralt current containing waste gases from a lime kiln, or similar source of carbon dioxid, is especially Well adapted since it is richer in carbon monoxid than producer gas made either with a straight air draft er with a dralt containing ordinary products of combustion. However, for reasons later apllo pearing, it is preferred to prepare the producer gas with waste gases from the formate. manufacture.

Where a white formate is desirable, the gas should be washed before/ use unless it be made from a producer charge of coke o1' charcoal.

ln performing the formate s \11tl.esis,-the carbonate is suspended in water in a vessel capable of resisting lieavy pressure, and earbon monoxid, or producer gas, introdmxed under a pressure of several atmospheres. The temperature in the vessel should be high. lemperature and pressure are in some degree reciprocal or interchange: ble, it being per-l missible to lower the temperature somewhat if the pressure be heightened and vice versa. A temperature of 2750 (l. and two or three atmospheres, or higher, may be employed. The should be blown in at the bottom of the digester to keep the carbonate in suspension .and insurey good contact, and the carbon dioxid, together witn the nitrogen of the producer gas, liberated at the top of the vessel through a suitable valved conduit. As it is desirable to work rapidly and to keep an excess of carbon monoxid present. at all times, there is commonly more. or less of this substance in the waste gases. l`o eeonomize it therefore, the. waste gases may bc usefully employed as a component of the. draft current of' the producer. lnder the ordinary laws of mass action, governing such reactions as this, it is desirable. to keep an excess of the reacting bodies present at all times and avoid an excess of the product of reaction. this reason, the producer. is ordinarily blown through faster than it is absorbed and since the unabsorbed portion goes back to the )roducer in this embodiment of this in vention this can be very advantageously done, keeping a high partial. pressure of car* bon monoxid in the. formate vessel at' all tim'es without waste. Further, an exeess'of insoluble carbonate is also desirable. There# fore, the operation is` interrupted from time to time, the excess of carbonate allowed to settle out, and the produced forinate removed by drawing oilI a portion of the. solution, which is replaced by fresh water. Thus operating it is obvious that there is at all times an excess of the reacting bodies while any large excess of the product of reaction, the formate, is avoided.. These conditions contribute materially to thespeed and practicality of the process.

ln blowing air'through a deep bed of ignited fuel in a gas producer, they oxygen. isneairly all converted into carbon monoxid,` and the gasr produced consists essentially of a mixture of monoxid and nitrogen,. though it always con tains a small amount of carbon dioxid', the proportion demanded by the laws of' partial pressures.under the temperatures and other conditions existing in the producer. But

For

causing the issuing gas to be unduly hot, raising its tenor in carbon dioxid, ete. For this reason it is desirable to balance the heat evolving properties of air b v constituting the draftcurrent partly of carbon dioxidy or gases containing the same, since the reduction of the dioxid by carbon yaliisorbs heat, thereby maintaining the heat of the producer at any desired point. his carbondioxid may very advantageously be that evolved in the formate reaction, thereby ineidentally recoveringl carbon monoxid which has gone through the formate digester unchanged. VVhere work in the digester is pushed and much carbon monoxid passes through unehanged,'in order to avoid an explosive mixture the air Afor the draft current and the digester gases may be introduced into the producer through separate twycrs, located however in close proximity so that exothermic and endothermic reactions may balance eacn. other in the same layers of producer fuel.

In the preferred embodiment of this invention, the waste gases from the digester are used as the endotlwrmic agent for tne salie of recovering carbon monox'id, since with this gas so utilized a rapid circulation can be. maintained through the. digester without waste. The proportions of these waste gases and of air in the draft current are preferably so balanced that the, fuel in thc producer is maintained at an efficient gasifying temperature.

Before use the waste. gases from the digester are preferably cooled or refrigerated or otherwise Vtreated to free them from water vapor for the reason that steam in the produc-er forms hydrogen and this is, as stated, undesirable. in the gas furnishedthe digester. Moisture in the draft current is also apt to result in undesirable amounts of carbon dioxid in the gas.

ln the accompanying, more or less dia- `gran'unatie, drawing' is 1 shown one form of Aapparatus of 'the many adapted to perform the process of the present inyention.

In this illustration: his a gas producer provided with the usual fuel inlet and water seal t is a gas conduit and 5 the draft inlet pipe. This pipe is provided with fan-6 on the suction side of which is a valved air inlet 7.- The gas conduit is provided with a scrubber, 26 and an ordinary high pressure pump, 8, provided with the usual steam cylinder 8, taking gas from 4the conduit and delivering it through reheater 27 into the base of the digester 9 at 10 under high pressure. ln the.

1 d'igester the suspension of the. carbomite,v or l the formation of a thin magma is effected by since. the formation of monoxid is an exofor many reasons as tending to elinl er ash,`

f purpose in a dip of the pipe.

cranes y upper gate lo, a venting valve 1 7, and a.

valved equalizingpipe 18 establishing communication with the digester and equalizing pressures when feed is necessary. The Waste gases from the digester leave through valved' pipe lll provided withn a cooling-jacket 20 whereby water may be condensed out and removed, outlet 21 being provided for this lWhere a portion of the of the producer is used for other purposes all the Waste gases from the digester may rle .returned thereto. lf used only for the formate digester, thc'eXcess of waste gases above that needed an endothermic agent in the producer ymay depart through valved pipe it the lowermost portieri of the digester is a sandgate 22 for removing sand, etc., entering with the carbonate and accumulating. ltt. a point Well above the bottom of the digester is a valved liquid outlet pipe 23 communicating with a vacuum pan or other form of evaporator, 24;. r.

Steam pipes 25 provide the necessary heat in the dig-ester.

in operation, a mixture of"carbonate, or

other insoluble basic body, and ,Water is introduced `into the digester till the desired liquid level is attained and gas from the producer is forced in underl high pressure, bubbling through the magma of 'Water and base and converting it intoaJ solution of formate of the base employed. The carbonio acid displaced,` When a carbonate is used, the nitrogen' of the gas and Whatever carbon A inonoilid has not been absorbed leavethe digestor as Waste gases. lhese Waste gases are cooled and all or a fraction used to admin with the air employed for the draft currentof the producer. i As the Water in the digester becomes charged with formate, the admission of gas is stopped from time to time whereby the liquid in the digester becornes quiet and. the suspended insoluble base settles to the bottom Ideriving a comn parativcly clear liquid above. lrlhen cal* cium form-ate is being produced, the solution maybe drarvnoff at about 5 to (3 per cent. for-V mate content. lf a stirring mechanism is also used it is of course stoppcdduring this settling period: The clear. liquid is drawn off, sent to the evaporator, fresh Water and base athled andthe introduction of gas resumed. T he speed of gas circulation will Vdepend somewhat onthe particular carbonate employed and therpartial pressure of carbon monorid which it is desirable to maintain in theforinate vessel7 but ordinarily'the to result in about per cent. absorption of the carbon monoxid. "W hat We claim is:

l. ln the manufacture of form ates, the process Which consists in suspending in Water a metallic basic body substantially insoluble in Water, treating said suspended body with carbon monoxid under high pressure and at a high temperature till a formate is formed in substantial amount, allowing the excess of basic body to settle out of the clear solution so formed, removing a portion of the solution, replacing Withwater and repeating the operation.

2. ln the manufacture of formatos, the process which consists -in treating an insolublef carbonate suspended in Water With carbon monoxid at a high temperature and un der high pressure.

,ln the manufacture Vof formates, the process which consists in treating an insolu ble metallic carbonate suspended inwater of hightemperature with carbonmonoxid under pressure. l. lfn the manufacture of formates, the process which consists in treating an insoluble metallic carbonate suspended in Water of pressure;

5. ln the manufacture of calcium formate,

carbonate suspended in Water with carbon monoxid at a high temperature and under high pressure. V

ln the manufactureof calcium formate, the process which consists in treatin@ calcium carbonate suspended in Water ofngh tem perature with carbon monoxid under pressure.

the process which consists in treating calcium .carbonate suspended in Water of high temperature with producer gas, under high pressure.

` 8. ln the manufacture of calcium. formate, the process which consists in tre ating calcium carbonate suspended in Water of high temperature with producer gesunder pressure. t). The process of manufacturing formatos which consists in treating a basic body suspended in Water 'of high temperature with a current of producer gas under pressure at a rate faster than the basic body Will absorb carbon mon oxid therefrom, removing the encess and Waste admixing the same With air, transmitting the same through a deep bed of ignited fuel andreturning the resultant gas into contact with aforesaid basic body.

l0. The process of manufacturing formates which consists in treating an insoluble metal lic carlionz'tte suspended in Water of high temperature `with producer gas under pressure,

ing the same With air, transmitting the same high temperature With producer gas under the process Which consists in treating calcium 7. In the manufacture of calcium formate,

removing the excess and waste gases, admini through adeep bed of ignited fuel and returning the resultant gas into contact with aforesaid carbonate. u i

1i. The process ofmanufacturing calcium formate which consists in treatinO calcium carbonate suspended in water of" ugh temperature with producer gas under pressure7 `substantially insoluble in water, said ina-gmabeing maintained under high temperature and pressure, ceasing the introduction of" Jthe gas when the water becomes chargedV with 'formate and before all the base is converted, allowing the base in excess to settle and withdrawing a portion of the clear solution.

13. The process of producing calcium formate which consists in 'forcing carbon nionoxid through a magma of water and calcium 'carbonate maintained under li igh temperai; crepes ture and pressure, ceasing the introduction of the gas when the water becomes charged with formate and before all the calcium carbonario is converted, allowingl the carbonate l in excess to settle out and withdrawing a poi'- tion of the clear liquid.A

14. The process of producing calcium 4ierinate which consist'sin forcing carbon nionoxid through a magma of water and vrccipitated calcium carbonate maintained under high temperature and pressure, ceasing the introduction of the gas when the water becomes charged with formate and before all the calcium carbonate is converted, allowing the carbonate in excess to settle out and withdrawing a portion of the clear liquid.

ln testimony whereof, we aflix our signatures. in tlie presence of witnesses.

(TA llillON ELLIS. K. il. MGELRUY. Witnesses for Ellis: T. il. FAIR, FLETCHER P. Sooriiirn. l.Witnesses for McElroy: p

BLANCHE L. CiiAinv'nLL, A. M.. HoUGnTon. 

